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Elements of Chemistry, - In a New Systematic Order, Containing all the Modern Discoveries
by Antoine Lavoisier
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By a contrary supposition to the one we have been forming, if the earth were suddenly transported into a very cold region, the water which at present composes our seas, rivers, and springs, and probably the greater number of the fluids we are acquainted with, would be converted into solid mountains and hard rocks, at first diaphanous and homogeneous, like rock crystal, but which, in time, becoming mixed with foreign and heterogeneous substances, would become opake stones of various colours. In this case, the air, or at least some part of the aeriform fluids which now compose the mass of our atmosphere, would doubtless lose its elasticity for want of a sufficient temperature to retain them in that state: They would return to the liquid state of existence, and new liquids would be formed, of whose properties we cannot, at present, form the most distant idea.

These two opposite suppositions give a distinct proof of the following corollaries: First, That solidity, liquidity, and aeriform elasticity, are only three different states of existence of the same matter, or three particular modifications which almost all substances are susceptible of assuming successively, and which solely depend upon the degree of temperature to which they are exposed; or, in other words, upon the quantity of caloric with which they are penetrated[8]. 2dly, That it is extremely probable that air is a fluid naturally existing in a state of vapour; or, as we may better express it, that our atmosphere is a compound of all the fluids which are susceptible of the vaporous or permanently elastic state, in the usual temperature, and under the common pressure. 3dly, That it is not impossible we may discover, in our atmosphere, certain substances naturally very compact, even metals themselves; as a metallic substance, for instance, only a little more volatile than mercury, might exist in that situation.

Amongst the fluids with which we are acquainted, some, as water and alkohol, are susceptible of mixing with each other in all proportions; whereas others, on the contrary, as quicksilver, water, and oil, can only form a momentary union; and, after being mixed together, separate and arrange themselves according to their specific gravities. The same thing ought to, or at least may, take place in the atmosphere. It is possible, and even extremely probable, that, both at the first creation, and every day, gasses are formed, which are difficultly miscible with atmospheric air, and are continually separating from it. If these gasses be specifically lighter than the general atmospheric mass, they must, of course, gather in the higher regions, and form strata that float upon the common air. The phenomena which accompany igneous meteors induce me to believe, that there exists in the upper parts of our atmosphere a stratum of inflammable fluid in contact with those strata of air which produce the phenomena of the aurora borealis and other fiery meteors.—I mean hereafter to pursue this subject in a separate treatise.

FOOTNOTES:

[8] The degree of pressure which they undergo must be taken into account. E.



CHAP. III.

Analysis of Atmospheric Air, and its Division into two Elastic Fluids; the one fit for Respiration, the other incapable of being respired.

From what has been premised, it follows, that our atmosphere is composed of a mixture of every substance capable of retaining the gasseous or aeriform state in the common temperature, and under the usual pressure which it experiences. These fluids constitute a mass, in some measure homogeneous, extending from the surface of the earth to the greatest height hitherto attained, of which the density continually decreases in the inverse ratio of the superincumbent weight. But, as I have before observed, it is possible that this first stratum is surmounted by several others consisting of very different fluids.

Our business, in this place, is to endeavour to determine, by experiments, the nature of the elastic fluids which compose the inferior stratum of air which we inhabit. Modern chemistry has made great advances in this research; and it will appear by the following details that the analysis of atmospherical air has been more rigorously determined than that of any other substance of the class. Chemistry affords two general methods of determining the constituent principles of bodies, the method of analysis, and that of synthesis. When, for instance, by combining water with alkohol, we form the species of liquor called, in commercial language, brandy or spirit of wine, we certainly have a right to conclude, that brandy, or spirit of wine, is composed of alkohol combined with water. We can produce the same result by the analytical method; and in general it ought to be considered as a principle in chemical science, never to rest satisfied without both these species of proofs.

We have this advantage in the analysis of atmospherical air, being able both to decompound it, and to form it a new in the most satisfactory manner. I shall, however, at present confine myself to recount such experiments as are most conclusive upon this head; and I may consider most of these as my own, having either first invented them, or having repeated those of others, with the intention of analysing atmospherical air, in perfectly new points of view.

I took a matrass (A, fig. 14. plate II.) of about 36 cubical inches capacity, having a long neck B C D E, of six or seven lines internal diameter, and having bent the neck as in Plate IV. Fig. 2. so as to allow of its being placed in the furnace M M N N, in such a manner that the extremity of its neck E might be inserted under a bell-glass F G, placed in a trough of quicksilver R R S S; I introduced four ounces of pure mercury into the matrass, and, by means of a syphon, exhausted the air in the receiver F G, so as to raise the quicksilver to L L, and I carefully marked the height at which it stood by pasting on a slip of paper. Having accurately noted the height of the thermometer and barometer, I lighted a fire in the furnace M M N N, which I kept up almost continually during twelve days, so as to keep the quicksilver always almost at its boiling point. Nothing remarkable took place during the first day: The Mercury, though not boiling, was continually evaporating, and covered the interior surface of the vessels with small drops, at first very minute, which gradually augmenting to a sufficient size, fell back into the mass at the bottom of the vessel. On the second day, small red particles began to appear on the surface of the mercury, which, during the four or five following days, gradually increased in size and number; after which they ceased to increase in either respect. At the end of twelve days, seeing that the calcination of the mercury did not at all increase, I extinguished the fire, and allowed the vessels to cool. The bulk of air in the body and neck of the matrass, and in the bell-glass, reduced to a medium of 28 inches of the barometer and 10 deg. (54.5 deg.) of the thermometer, at the commencement of the experiment was about 50 cubical inches. At the end of the experiment the remaining air, reduced to the same medium pressure and temperature, was only between 42 and 43 cubical inches; consequently it had lost about 1/6 of its bulk. Afterwards, having collected all the red particles, formed during the experiment, from the running mercury in which they floated, I found these to amount to 45 grains.

I was obliged to repeat this experiment several times, as it is difficult in one experiment both to preserve the whole air upon which we operate, and to collect the whole of the red particles, or calx of mercury, which is formed during the calcination. It will often happen in the sequel, that I shall, in this manner, give in one detail the results of two or three experiments of the same nature.

The air which remained after the calcination of the mercury in this experiment, and which was reduced to 5/6 of its former bulk, was no longer fit either for respiration or for combustion; animals being introduced into it were suffocated in a few seconds, and when a taper was plunged into it, it was extinguished as if it had been immersed into water.

In the next place, I took the 45 grains of red matter formed during this experiment, which I put into a small glass retort, having a proper apparatus for receiving such liquid, or gasseous product, as might be extracted: Having applied a fire to the retort in a furnace, I observed that, in proportion as the red matter became heated, the intensity of its colour augmented. When the retort was almost red hot, the red matter began gradually to decrease in bulk, and in a few minutes after it disappeared altogether; at the same time 41-1/2 grains of running mercury were collected in the recipient, and 7 or 8 cubical inches of elastic fluid, greatly more capable of supporting both respiration and combustion than atmospherical air, were collected in the bell-glass.

A part of this air being put into a glass tube of about an inch diameter, showed the following properties: A taper burned in it with a dazzling splendour, and charcoal, instead of consuming quietly as it does in common air, burnt with a flame, attended with a decrepitating noise, like phosphorus, and threw out such a brilliant light that the eyes could hardly endure it. This species of air was discovered almost at the same time by Mr Priestley, Mr Scheele, and myself. Mr Priestley gave it the name of dephlogisticated air, Mr Scheele called it empyreal air. At first I named it highly respirable air, to which has since been substituted the term of vital air. We shall presently see what we ought to think of these denominations.

In reflecting upon the circumstances of this experiment, we readily perceive, that the mercury, during its calcination, absorbs the salubrious and respirable part of the air, or, to speak more strictly, the base of this respirable part; that the remaining air is a species of mephitis, incapable of supporting combustion or respiration; and consequently that atmospheric air is composed of two elastic fluids of different and opposite qualities. As a proof of this important truth, if we recombine these two elastic fluids, which we have separately obtained in the above experiment, viz. the 42 cubical inches of mephitis, with the 8 cubical inches of respirable air, we reproduce an air precisely similar to that of the atmosphere, and possessing nearly the same power of supporting combustion and respiration, and of contributing to the calcination of metals.

Although this experiment furnishes us with a very simple means of obtaining the two principal elastic fluids which compose our atmosphere, separate from each other, yet it does not give us an exact idea of the proportion in which these two enter into its composition: For the attraction of mercury to the respirable part of the air, or rather to its base, is not sufficiently strong to overcome all the circumstances which oppose this union. These obstacles are the mutual adhesion of the two constituent parts of the atmosphere for each other, and the elective attraction which unites the base of vital air with caloric; in consequence of these, when the calcination ends, or is at least carried as far as is possible, in a determinate quantity of atmospheric air, there still remains a portion of respirable air united to the mephitis, which the mercury cannot separate. I shall afterwards show, that, at least in our climate, the atmospheric air is composed of respirable and mephitic airs, in the proportion of 27 and 73; and I shall then discuss the causes of the uncertainty which still exists with respect to the exactness of that proportion.

Since, during the calcination of mercury, air is decomposed, and the base of its respirable part is fixed and combined with the mercury, it follows, from the principles already established, that caloric and light must be disengaged during the process: But the two following causes prevent us from being sensible of this taking place: As the calcination lasts during several days, the disengagement of caloric and light, spread out in a considerable space of time, becomes extremely small for each particular moment of that time, so as not to be perceptible; and, in the next place, the operation being carried on by means of fire in a furnace, the heat produced by the calcination itself becomes confounded with that proceeding from the furnace. I might add the respirable part of the air, or rather its base, in entering into combination with the mercury, does not part with all the caloric which it contained, but still retains a part of it after forming the new compound; but the discussion of this point, and its proofs from experiment, do not belong to this part of our subject.

It is, however, easy to render this disengagement of caloric and light evident to the senses, by causing the decomposition of air to take place in a more rapid manner. And for this purpose, iron is excellently adapted, as it possesses a much stronger affinity for the base of respirable air than mercury. The elegant experiment of Mr Ingenhouz, upon the combustion of iron, is well known. Take a piece of fine iron wire, twisted into a spiral, (BC, Plate IV. Fig. 17.) fix one of its extremities B into the cork A, adapted to the neck of the bottle DEFG, and fix to the other extremity of the wire C, a small morsel of tinder. Matters being thus prepared, fill the bottle DEFG with air deprived of its mephitic part; then light the tinder, and introduce it quickly with the wire upon which it is fixed, into the bottle which you stop up with the cork A, as is shown in the figure (17 Plate IV.) The instant the tinder comes into contact with the vital air it begins to burn with great intensity; and, communicating the inflammation to the iron-wire, it too takes fire, and burns rapidly, throwing out brilliant sparks, which fall to the bottom of the vessel in rounded globules, which become black in cooling, but retain a degree of metallic splendour. The iron thus burnt is more brittle even than glass, and is easily reduced into powder, and is still attractable by the magnet, though not so powerfully as it was before combustion. As Mr Ingenhouz has neither examined the change produced on iron, nor upon the air by this operation, I have repeated the experiment under different circumstances, in an apparatus adapted to answer my particular views, as follows.

Having filled a bell-glass (A, Plate IV. Fig. 3.) of about six pints measure, with pure air, or the highly respirable part of air, I transported this jar by means of a very flat vessel, into a quicksilver bath in the bason BC, and I took care to render the surface of the mercury perfectly dry both within and without the jar with blotting paper. I then provided a small capsule of china-ware D, very flat and open, in which I placed some small pieces of iron, turned spirally, and arranged in such a way as seemed most favourable for the combustion being communicated to every part. To the end of one of these pieces of iron was fixed a small morsel of tinder, to which was added about the sixteenth part of a grain of phosphorus, and, by raising the bell-glass a little, the china capsule, with its contents, were introduced into the pure air. I know that, by this means, some common air must mix with the pure air in the glass; but this, when it is done dexterously, is so very trifling, as not to injure the success of the experiment. This being done, a part of the air is sucked out from the bell-glass, by means of a syphon GHI, so as to raise the mercury within the glass to EF; and, to prevent the mercury from getting into the syphon, a small piece of paper is twisted round its extremity. In sucking out the air, if the motion of the lungs only be used, we cannot make the mercury rise above an inch or an inch and a half; but, by properly using the muscles of the mouth, we can, without difficulty, cause it to rise six or seven inches.

I next took an iron wire, (MN, Plate IV. Fig. 16.) properly bent for the purpose, and making it red hot in the fire, passed it through the mercury into the receiver, and brought it in contact with the small piece of phosphorus attached to the tinder. The phosphorus instantly takes fire, which communicates to the tinder, and from that to the iron. When the pieces have been properly arranged, the whole iron burns, even to the last particle, throwing out a white brilliant light similar to that of Chinese fireworks. The great heat produced by this combustion melts the iron into round globules of different sizes, most of which fall into the China cup; but some are thrown out of it, and swim upon the surface of the mercury. At the beginning of the combustion, there is a slight augmentation in the volume of the air in the bell-glass, from the dilatation caused by the heat; but, presently afterwards, a rapid diminution of the air takes place, and the mercury rises in the glass; insomuch that, when the quantity of iron is sufficient, and the air operated upon is very pure, almost the whole air employed is absorbed.

It is proper to remark in this place, that, unless in making experiments for the purpose of discovery, it is better to be contented with burning a moderate quantity of iron; for, when this experiment is pushed too far, so as to absorb much of the air, the cup D, which floats upon the quicksilver, approaches too near the bottom of the bell-glass; and the great heat produced, which is followed by a very sudden cooling, occasioned by the contact of the cold mercury, is apt to break the glass. In which case, the sudden fall of the column of mercury, which happens the moment the least flaw is produced in the glass, causes such a wave, as throws a great part of the quicksilver from the bason. To avoid this inconvenience, and to ensure success to the experiment, one gross and a half of iron is sufficient to burn in a bell-glass, which holds about eight pints of air. The glass ought likewise to be strong, that it may be able to bear the weight of the column of mercury which it has to support.

By this experiment, it is not possible to determine, at one time, both the additional weight acquired by the iron, and the changes which have taken place in the air. If it is wished to ascertain what additional weight has been gained by the iron, and the proportion between that and the air absorbed, we must carefully mark upon the bell-glass, with a diamond, the height of the mercury, both before and after the experiment[9]. After this, the syphon (GH, Pl. IV. fig. 3.) guarded, as before, with a bit of paper, to prevent its filling with mercury, is to be introduced under the bell-glass, having the thumb placed upon the extremity, G, of the syphon, to regulate the passage of the air; and by this means the air is gradually admitted, so as to let the mercury fall to its level. This being done, the bell-glass is to be carefully removed, the globules of melted iron contained in the cup, and those which have been scattered about, and swim upon the mercury, are to be accurately collected, and the whole is to be weighed. The iron will be found in that state called martial ethiops by the old chemists, possessing a degree of metallic brilliancy, very friable, and readily reducible into powder, under the hammer, or with a pestle and mortar. If the experiment has succeeded well, from 100 grains of iron will be obtained 135 or 136 grains of ethiops, which is an augmentation of 35 per cent.

If all the attention has been paid to this experiment which it deserves, the air will be found diminished in weight exactly equal to what the iron has gained. Having therefore burnt 100 grains of iron, which has acquired an additional weight of 35 grains, the diminution of air will be found exactly 70 cubical inches; and it will be found, in the sequel, that the weight of vital air is pretty nearly half a grain for each cubical inch; so that, in effect, the augmentation of weight in the one exactly coincides with the loss of it in the other.

I shall observe here, once for all, that, in every experiment of this kind, the pressure and temperature of the air, both before and after the experiment, must be reduced, by calculation, to a common standard of 10 deg. (54.5 deg.) of the thermometer, and 28 inches of the barometer. Towards the end of this work, the manner of performing this very necessary reduction will be found accurately detailed.

If it be required to examine the nature of the air which remains after this experiment, we must operate in a somewhat different manner. After the combustion is finished, and the vessels have cooled, we first take out the cup, and the burnt iron, by introducing the hand through the quicksilver, under the bell-glass; we next introduce some solution of potash, or caustic alkali, or of the sulphuret of potash, or such other substance as is judged proper for examining their action upon the residuum of air. I shall, in the sequel, give an account of these methods of analysing air, when I have explained the nature of these different substances, which are only here in a manner accidentally mentioned. After this examination, so much water must be let into the glass as will displace the quicksilver, and then, by means of a shallow dish placed below the bell-glass, it is to be removed into the common water pneumato-chemical apparatus, where the air remaining may be examined at large, and with great facility.

When very soft and very pure iron has been employed in this experiment, and, if the combustion has been performed in the purest respirable or vital air, free from all admixture of the noxious or mephitic part, the air which remains after the combustion will be found as pure as it was before; but it is difficult to find iron entirely free from a small portion of charry matter, which is chiefly abundant in steel. It is likewise exceedingly difficult to procure the pure air perfectly free from some admixture of mephitis, with which it is almost always contaminated; but this species of noxious air does not, in the smallest degree, disturb the result of the experiment, as it is always found at the end exactly in the same proportion as at the beginning.

I mentioned before, that we have two ways of determining the constituent parts of atmospheric air, the method of analysis, and that by synthesis. The calcination of mercury has furnished us with an example of each of these methods, since, after having robbed the respirable part of its base, by means of the mercury, we have restored it, so as to recompose an air precisely similar to that of the atmosphere. But we can equally accomplish this synthetic composition of atmospheric air, by borrowing the materials of which it is composed from different kingdoms of nature. We shall see hereafter that, when animal substances are dissolved in the nitric acid, a great quantity of gas is disengaged, which extinguishes light, and is unfit for animal respiration, being exactly similar to the noxious or mephitic part of atmospheric air. And, if we take 73 parts, by weight, of this elastic fluid, and mix it with 27 parts of highly respirable air, procured from calcined mercury, we will form an elastic fluid precisely similar to atmospheric air in all its properties.

There are many other methods of separating the respirable from the noxious part of the atmospheric air, which cannot be taken notice of in this part, without anticipating information, which properly belongs to the subsequent chapters. The experiments already adduced may suffice for an elementary treatise; and, in matters of this nature, the choice of our evidences is of far greater consequence than their number.

I shall close this article, by pointing out the property which atmospheric air, and all the known gasses, possess of dissolving water, which is of great consequence to be attended to in all experiments of this nature. Mr Saussure found, by experiment, that a cubical foot of atmospheric air is capable of holding 12 grains of water in solution: Other gasses, as the carbonic acid, appear capable of dissolving a greater quantity; but experiments are still wanting by which to determine their several proportions. This water, held in solution by gasses, gives rise to particular phenomena in many experiments, which require great attention, and which has frequently proved the source of great errors to chemists in determining the results of their experiments.

FOOTNOTES:

[9] It will likewise be necessary to take care that the air contained in the glass, both before and after the experiment, be reduced to a common temperature and pressure, otherwise the results of the following calculations will be fallacious.—E.



CHAP. IV.

Nomenclature of the several Constituent Parts of Atmospheric Air.

Hitherto I have been obliged to make use of circumlocution, to express the nature of the several substances which constitute our atmosphere, having provisionally used the terms of respirable and noxious, or non-respirable parts of the air. But the investigations I mean to undertake require a more direct mode of expression; and, having now endeavoured to give simple and distinct ideas of the different substances which enter into the composition of the atmosphere, I shall henceforth express these ideas by words equally simple.

The temperature of our earth being very near to that at which water becomes solid, and reciprocally changes from solid to fluid, and as this phenomenon takes place frequently under our observation, it has very naturally followed, that, in the languages of at least every climate subjected to any degree of winter, a term has been used for signifying water in the state of solidity, when deprived of its caloric. The same, however, has not been found necessary with respect to water reduced to the state of vapour by an additional dose of caloric; since those persons who do not make a particular study of objects of this kind, are still ignorant that water, when in a temperature only a little above the boiling heat, is changed into an elastic aeriform fluid, susceptible, like all other gasses, of being received and contained in vessels, and preserving its gasseous form so long as it remains at the temperature of 80 deg. (212 deg.), and under a pressure not exceeding 28 inches of the mercurial barometer. As this phenomenon has not been generally observed, no language has used a particular term for expressing water in this state[10]; and the same thing occurs with all fluids, and all substances, which do not evaporate in the common temperature, and under the usual pressure of our atmosphere.

For similar reasons, names have not been given to the liquid or concrete states of most of the aeriform fluids: These were not known to arise from the combination of caloric with certain bases; and, as they had not been seen either in the liquid or solid states, their existence, under these forms, was even unknown to natural philosophers.

We have not pretended to make any alteration upon such terms as are sanctified by ancient custom; and, therefore, continue to use the words water and ice in their common acceptation: We likewise retain the word air, to express that collection of elastic fluids which composes our atmosphere; but we have not thought it necessary to preserve the same respect for modern terms, adopted by latter philosophers, having considered ourselves as at liberty to reject such as appeared liable to occasion erroneous ideas of the substances they are meant to express, and either to substitute new terms, or to employ the old ones, after modifying them in such a manner as to convey more determinate ideas. New words have been drawn, chiefly from the Greek language, in such a manner as to make their etymology convey some idea of what was meant to be represented; and these we have always endeavoured to make short, and of such a nature as to be changeable into adjectives and verbs.

Following these principles, we have, after Mr Macquer's example, retained the term gas, employed by Vanhelmont, having arranged the numerous class of elastic aeriform fluids under that name, excepting only atmospheric air. Gas, therefore, in our nomenclature, becomes a generic term, expressing the fullest degree of saturation in any body with caloric; being, in fact, a term expressive of a mode of existence. To distinguish each species of gas, we employ a second term from the name of the base, which, saturated with caloric, forms each particular gas. Thus, we name water combined to saturation with caloric, so as to form an elastic fluid, aqueous gas; ether, combined in the same manner, etherial gas; the combination of alkohol with caloric, becomes alkoholic gas; and, following the same principles, we have muriatic acid gas, ammoniacal gas, and so on of every substance susceptible of being combined with caloric, in such a manner as to assume the gasseous or elastic aeriform state.

We have already seen, that the atmospheric air is composed of two gasses, or aeriform fluids, one of which is capable, by respiration, of contributing to animal life, and in which metals are calcinable, and combustible bodies may burn; the other, on the contrary, is endowed with directly opposite qualities; it cannot be breathed by animals, neither will it admit of the combustion of inflammable bodies, nor of the calcination of metals. We have given to the base of the former, or respirable portion of the air, the name of oxygen, from [Greek: oxys] acidum, and [Greek: geinomas], gignor; because, in reality, one of the most general properties of this base is to form acids, by combining with many different substances. The union of this base with caloric we term oxygen gas, which is the same with what was formerly called pure, or vital air. The weight of this gas, at the temperature of 10 deg. (54.50), and under a pressure equal to 28 inches of the barometer, is half a grain for each cubical inch, or one ounce and a half to each cubical foot.

The chemical properties of the noxious portion of atmospheric air being hitherto but little known, we have been satisfied to derive the name of its base from its known quality of killing such animals as are forced to breathe it, giving it the name of azote, from the Greek privitive particle [Greek: a] and [Greek: xae], vita; hence the name of the noxious part of atmospheric air is azotic gas; the weight of which, in the same temperature, and under the same pressure, is 1 oz. 2 gros and 48 grs. to the cubical foot, or 0.4444 of a grain to the cubical inch. We cannot deny that this name appears somewhat extraordinary; but this must be the case with all new terms, which cannot be expected to become familiar until they have been some time in use. We long endeavoured to find a more proper designation without success; it was at first proposed to call it alkaligen gas, as, from the experiments of Mr Berthollet, it appears to enter into the composition of ammoniac, or volatile alkali; but then, we have as yet no proof of its making one of the constituent elements of the other alkalies; beside, it is proved to compose a part of the nitric acid, which gives as good reason to have called it nitrigen. For these reasons, finding it necessary to reject any name upon systematic principles, we have considered that we run no risk of mistake in adopting the terms of azote, and azotic gas, which only express a matter of fact, or that property which it possesses, of depriving such animals as breathe it of their lives.

I should anticipate subjects more properly reserved for the subsequent chapters, were I in this place to enter upon the nomenclature of the several species of gasses: It is sufficient, in this part of the work, to establish the principles upon which their denominations are founded. The principal merit of the nomenclature we have adopted is, that, when once the simple elementary substance is distinguished by an appropriate term, the names of all its compounds derive readily, and necessarily, from this first denomination.

FOOTNOTES:

[10] In English, the word steam is exclusively appropriated to water in the state of vapour. E.



CHAP. V.

Of the Decomposition of Oxygen Gas by Sulphur, Phosphorus, and Charcoal—and of the Formation of Acids in general.

In performing experiments, it is a necessary principle, which ought never to be deviated from, that they be simplified as much as possible, and that every circumstance capable of rendering their results complicated be carefully removed. Wherefore, in the experiments which form the object of this chapter, we have never employed atmospheric air, which is not a simple substance. It is true, that the azotic gas, which forms a part of its mixture, appears to be merely passive during combustion and calcination; but, besides that it retards these operations very considerably, we are not certain but it may even alter their results in some circumstances; for which reason, I have thought it necessary to remove even this possible cause of doubt, by only making use of pure oxygen gas in the following experiments, which show the effects produced by combustion in that gas; and I shall advert to such differences as take place in the results of these, when the oxygen gas, or pure vital air, is mixed, in different proportions, with azotic gas.

Having filled a bell-glass (A. Pl. iv. fig. 3), of between five and six pints measure, with oxygen gas, I removed it from the water trough, where it was filled, into the quicksilver bath, by means of a shallow glass dish slipped underneath, and having dried the mercury, I introduced 61-1/4 grains of Kunkel's phosphorus in two little China cups, like that represented at D, fig. 3. under the glass A; and that I might set fire to each of the portions of phosphorus separately, and to prevent the one from catching fire from the other, one of the dishes was covered with a piece of flat glass. I next raised the quicksilver in the bell-glass up to E F, by sucking out a sufficient portion of the gas by means of the syphon G H I. After this, by means of the crooked iron wire (fig. 16.), made red hot, I set fire to the two portions of phosphorus successively, first burning that portion which was not covered with the piece of glass. The combustion was extremely rapid, attended with a very brilliant flame, and considerable disengagement of light and heat. In consequence of the great heat induced, the gas was at first much dilated, but soon after the mercury returned to its level, and a considerable absorption of gas took place; at the same time, the whole inside of the glass became covered with white light flakes of concrete phosphoric acid.

At the beginning of the experiment, the quantity of oxygen gas, reduced, as above directed, to a common standard, amounted to 162 cubical inches; and, after the combustion was finished, only 23-1/4 cubical inches, likewise reduced to the standard, remained; so that the quantity of oxygen gas absorbed during the combustion was 138-3/4 cubical inches, equal to 69.375 grains.

A part of the phosphorus remained unconsumed in the bottom of the cups, which being washed on purpose to separate the acid, weighed about 16-1/4 grains; so that about 45 grains of phosphorus had been burned: But, as it is hardly possible to avoid an error of one or two grains, I leave the quantity so far qualified. Hence, as nearly 45 grains of phosphorus had, in this experiment, united with 69.375 grains of oxygen, and as no gravitating matter could have escaped through the glass, we have a right to conclude, that the weight of the substance resulting from the combustion in form of white flakes, must equal that of the phosphorus and oxygen employed, which amounts to 114.375 grains. And we shall presently find, that these flakes consisted entirely of a solid or concrete acid. When we reduce these weights to hundredth parts, it will be found, that 100 parts of phosphorus require 154 parts of oxygen for saturation, and that this combination will produce 254 parts of concrete phosphoric acid, in form of white fleecy flakes.

This experiment proves, in the most convincing manner, that, at a certain degree of temperature, oxygen possesses a stronger elective attraction, or affinity, for phosphorus than for caloric; that, in consequence of this, the phosphorus attracts the base of oxygen gas from the caloric, which, being set free, spreads itself over the surrounding bodies. But, though this experiment be so far perfectly conclusive, it is not sufficiently rigorous, as, in the apparatus described, it is impossible to ascertain the weight of the flakes of concrete acid which are formed; we can therefore only determine this by calculating the weights of oxygen and phosphorus employed; but as, in physics, and in chemistry, it is not allowable to suppose what is capable of being ascertained by direct experiment, I thought it necessary to rep at this experiment, as follows, upon a larger scale, and by means of a different apparatus.

I took a large glass baloon (A. Pl. iv. fig. 4.) with an opening three inches diameter, to which was fitted a crystal stopper ground with emery, and pierced with two holes for the tubes yyy, xxx. Before shutting the baloon with its stopper, I introduced the support BC, surmounted by the china cup D, containing 150 grs. of phosphorus; the stopper was then fitted to the opening of the baloon, luted with fat lute, and covered with slips of linen spread with quick-lime and white of eggs: When the lute was perfectly dry, the weight of the whole apparatus was determined to within a grain, or a grain and a half. I next exhausted the baloon, by means of an air pump applied to the tube XXX, and then introduced oxygen gas by means of the tube yyy, having a stop cock adapted to it. This kind of experiment is most readily and most exactly performed by means of the hydro-pneumatic machine described by Mr Meusnier and me in the Memoirs of the Academy for 1782, pag. 466. and explained in the latter part of this work, with several important additions and corrections since made to it by Mr Meusnier. With this instrument we can readily ascertain, in the most exact manner, both the quantity of oxygen gas introduced into the baloon, and the quantity consumed during the course of the experiment.

When all things were properly disposed, I set fire to the phosphorus with a burning glass. The combustion was extremely rapid, accompanied with a bright flame, and much heat; as the operation went on, large quantities of white flakes attached themselves to the inner surface of the baloon, so that at last it was rendered quite opake. The quantity of these flakes at last became so abundant, that, although fresh oxygen gas was continually supplied, which ought to have supported the combustion, yet the phosphorus was soon extinguished. Having allowed the apparatus to cool completely, I first ascertained the quantity of oxygen gas employed, and weighed the baloon accurately, before it was opened. I next washed, dried, and weighed the small quantity of phosphorus remaining in the cup, on purpose to determine the whole quantity of phosphorus consumed in the experiment; this residuum of the phosphorus was of a yellow ochrey colour. It is evident, that by these several precautions, I could easily determine, 1st, the weight of the phosphorus consumed; 2d, the weight of the flakes produced by the combustion; and, 3d, the weight of the oxygen which had combined with the phosphorus. This experiment gave very nearly the same results with the former, as it proved that the phosphorus, during its combustion, had absorbed a little more than one and a half its weight of oxygen; and I learned with more certainty, that the weight of the new substance, produced in the experiment, exactly equalled the sum of the weights of the phosphorus consumed, and oxygen absorbed, which indeed was easily determinable a priori. If the oxygen gas employed be pure, the residuum after combustion is as pure as the gas employed; this proves that nothing escapes from the phosphorus, capable of altering the purity of the oxygen gas, and that the only action of the phosphorus is to separate the oxygen from the caloric, with which it was before united.

I mentioned above, that when any combustible body is burnt in a hollow sphere of ice, or in an apparatus properly constructed upon that principle, the quantity of ice melted during the combustion is an exact measure of the quantity of caloric disengaged. Upon this head, the memoir given by M. de la Place and me, A(masculine ordinal). 1780, p. 355, may be consulted. Having submitted the combustion of phosphorus to this trial, we found that one pound of phosphorus melted a little more than 100 pounds of ice during its combustion.

The combustion of phosphorus succeeds equally well in atmospheric air as in oxygen gas, with this difference, that the combustion is vastly slower, being retarded by the large proportion of azotic gas mixed with the oxygen gas, and that only about one-fifth part of the air employed is absorbed, because as the oxygen gas only is absorbed, the proportion of the azotic gas becomes so great toward the close of the experiment, as to put an end to the combustion.

I have already shown, that phosphorus is changed by combustion into an extremely light, white, flakey matter; and its properties are entirely altered by this transformation: From being insoluble in water, it becomes not only soluble, but so greedy of moisture, as to attract the humidity of the air with astonishing rapidity; by this means it is converted into a liquid, considerably more dense, and of more specific gravity than water. In the state of phosphorus before combustion, it had scarcely any sensible taste, by its union with oxygen it acquires an extremely sharp and sour taste: in a word, from one of the class of combustible bodies, it is changed into an incombustible substance, and becomes one of those bodies called acids.

This property of a combustible substance to be converted into an acid, by the addition of oxygen, we shall presently find belongs to a great number of bodies: Wherefore, strict logic requires that we should adopt a common term for indicating all these operations which produce analogous results; this is the true way to simplify the study of science, as it would be quite impossible to bear all its specifical details in the memory, if they were not classically arranged. For this reason, we shall distinguish this conversion of phosphorus into an acid, by its union with oxygen, and in general every combination of oxygen with a combustible substance, by the term of oxygenation: from which I shall adopt the verb to oxygenate, and of consequence shall say, that in oxygenating phosphorus we convert it into an acid.

Sulphur is likewise a combustible body, or, in other words, it is a body which possesses the power of decomposing oxygen gas, by attracting the oxygen from the caloric with which it was combined. This can very easily be proved, by means of experiments quite similar to those we have given with phosphorus; but it is necessary to premise, that in these operations with sulphur, the same accuracy of result is not to be expected as with phosphorus; because the acid which is formed by the combustion of sulphur is difficultly condensible, and because sulphur burns with more difficulty, and is soluble in the different gasses. But I can safely assert, from my own experiments, that sulphur in burning absorbs oxygen gas; that the resulting acid is considerably heavier than the sulphur burnt; that its weight is equal to the sum of the weights of the sulphur which has been burnt, and of the oxygen absorbed; and, lastly that this acid is weighty, incombustible, and miscible with water in all proportions: The only uncertainty remaining upon this head, is with regard to the proportions of sulphur and of oxygen which enter into the composition of the acid.

Charcoal, which, from all our present knowledge regarding it, must be considered as a simple combustible body, has likewise the property of decomposing oxygen gas, by absorbing its base from the caloric: But the acid resulting from this combustion does not condense in the common temperature; under the pressure of our atmosphere, it remains in the state of gas, and requires a large proportion of water to combine with or be dissolved in. This acid has, however, all the known properties of other acids, though in a weaker degree, and combines, like them, with all the bases which are susceptible of forming neutral salts.

The combustion of charcoal in oxygen gas, may be effected like that of phosphorus in the bell-glass, (A. Pl. IV. fig. 3.) placed over mercury: but, as the heat of red hot iron is not sufficient to set fire to the charcoal, we must add a small morsel of tinder, with a minute particle of phosphorus, in the same manner as directed in the experiment for the combustion of iron. A detailed account of this experiment will be found in the memoirs of the academy for 1781, p. 448. By that experiment it appears, that 28 parts by weight of charcoal require 72 parts of oxygen for saturation, and that the aeriform acid produced is precisely equal in weight to the sum of the weights of the charcoal and oxygen gas employed. This aeriform acid was called fixed or fixable air by the chemists who first discovered it; they did not then know whether it was air resembling that of the atmosphere, or some other elastic fluid, vitiated and corrupted by combustion; but since it is now ascertained to be an acid, formed like all others by the oxygenation of its peculiar base, it is obvious that the name of fixed air is quite ineligible[11].

By burning charcoal in the apparatus mentioned p. 60, Mr de la Place and I found that one lib. of charcoal melted 96 libs. 6 oz. of ice; that, during the combustion, 2 libs. 9 oz. 1 gros. 10 grs. of oxygen were absorbed, and that 3 libs. 9 oz. 1 gros. 10 grs. of acid gas were formed. This gas weighs 0.695 parts of a grain for each cubical inch, in the common standard temperature and pressure mentioned above, so that 34,242 cubical inches of acid gas are produced by the combustion of one pound of charcoal.

I might multiply these experiments, and show by a numerous succession of facts, that all acids are formed by the combustion of certain substances; but I am prevented from doing so in place, by the plan which I have laid down, of proceeding only from facts already ascertained, to such as are unknown, and of drawing my examples only from circumstances already explained. In the mean time, however, the three examples above cited may suffice for giving a clear and accurate conception of the manner in which acids are formed. By these it may be clearly seen, that oxygen is an element common to them all, which constitutes their acidity; and that they differ from each other, according to the nature of the oxygenated or acidified substance. We must therefore, in every acid, carefully distinguish between the acidifiable, base, which Mr de Morveau calls the radical, and the acidifiing principle or oxygen.

FOOTNOTES:

[11] It may be proper to remark, though here omitted by the author, that, in conformity with the general principles of the new nomenclature, this acid is by Mr Lavoisier and his coleagues called the carbonic acid, and when in the aeriform state carbonic acid gas. E.



CHAP. VI.

Of the Nomenclature of Acids in general, and particularly of those drawn from Nitre and Sea-Salt.

It becomes extremely easy, from the principles laid down in the preceding chapter, to establish a systematic nomenclature for the acids: The word acid, being used as a generic term, each acid falls to be distinguished in language, as in nature, by the name of its base or radical. Thus, we give the generic name of acids to the products of the combustion or oxygenation of phosphorus, of sulphur, and of charcoal; and these products are respectively named, the phosphoric acid, the sulphuric acid, and the carbonic acid.

There is however, a remarkable circumstance in the oxygenation of combustible bodies, and of a part of such bodies as are convertible into acids, that they are susceptible of different degrees of saturation with oxygen, and that the resulting acids, though formed by the union of the same elements, are possessed of different properties, depending upon that difference of proportion. Of this, the phosphoric acid, and more especially the sulphuric, furnishes us with examples. When sulphur is combined with a small proportion of oxygen, it forms, in this first or lower degree of oxygenation, a volatile acid, having a penetrating odour, and possessed of very particular qualities. By a larger proportion of oxygen, it is changed into a fixed, heavy acid, without any odour, and which, by combination with other bodies, gives products quite different from those furnished by the former. In this instance, the principles of our nomenclature seem to fail; and it seems difficult to derive such terms from the name of the acidifiable base, as shall distinctly express these two degrees of saturation, or oxygenation, without circumlocution. By reflection, however, upon the subject, or perhaps rather from the necessity of the case, we have thought it allowable to express these varieties in the oxygenation of the acids, by simply varying the termination of their specific names. The volatile acid produced from sulphur was anciently known to Stahl under the name of sulphurous acid[12]. We have preserved that term for this acid from sulphur under-saturated with oxygen; and distinguish the other, or completely saturated or oxygenated acid, by the name of sulphuric acid. We shall therefore say, in this new chemical language, that sulphur, in combining with oxygen, is susceptible of two degrees of saturation; that the first, or lesser degree, constitutes sulphurous acid, which is volatile and penetrating; whilst the second, or higher degree of saturation, produces sulphuric acid, which is fixed and inodorous. We shall adopt this difference of termination for all the acids which assume several degrees of saturation. Hence we have a phosphorous and a phosphoric acid, an acetous and an acetic acid; and so on, for others in similar circumstances.

This part of chemical science would have been extremely simple, and the nomenclature of the acids would not have been at all perplexed, as it is now in the old nomenclature, if the base or radical of each acid had been known when the acid itself was discovered. Thus, for instance, phosphorus being a known substance before the discovery of its acid, this latter was rightly distinguished by a term drawn from the name of its acidifiable base. But when, on the contrary, an acid happened to be discovered before its base, or rather, when the acidifiable base from which it was formed remained unknown, names were adopted for the two, which have not the smallest connection; and thus, not only the memory became burthened with useless appellations, but even the minds of students, nay even of experienced chemists, became filled with false ideas, which time and reflection alone is capable of eradicating. We may give an instance of this confusion with respect to the acid sulphur: The former chemists having procured this acid from the vitriol of iron, gave it the name of the vitriolic acid from the name of the substance which produced it; and they were then ignorant that the acid procured from sulphur by combustion was exactly the same.

The same thing happened with the aeriform acid formerly called fixed air; it not being known that this acid was the result of combining charcoal with oxygen, a variety of denominations have been given to it, not one of which conveys just ideas of its nature or origin. We have found it extremely easy to correct and modify the ancient language with respect to these acids proceeding from known bases, having converted the name of vitriolic acid into that of sulphuric, and the name of fixed air into that of carbonic acid; but it is impossible to follow this plan with the acids whose bases are still unknown; with these we have been obliged to use a contrary plan, and, instead of forming the name of the acid from that of its base, have been forced to denominate the unknown base from the name of the known acid, as happens in the case of the acid which is procured from sea salt.

To disengage this acid from the alkaline base with which it is combined, we have only to pour sulphuric acid upon sea-salt, immediately a brisk effervescence takes place, white vapours arise, of a very penetrating odour, and, by only gently heating the mixture, all the acid is driven off. As, in the common temperature and pressure of our atmosphere, this acid is naturally in the state of gas, we must use particular precautions for retaining it in proper vessels. For small experiments, the most simple and most commodious apparatus consists of a small retort G, (Pl. V. Fig. 5.), into which the sea-salt is introduced, well dried[13], we then pour on some concentrated sulphuric acid, and immediately introduce the beak of the retort under little jars or bell-glasses A, (same Plate and Fig.), previously filled with quicksilver. In proportion as the acid gas is disengaged, it passes into the jar, and gets to the top of the quicksilver, which it displaces. When the disengagement of the gas slackens, a gentle heat is applied to the retort, and gradually increased till nothing more passes over. This acid gas has a very strong affinity with water, which absorbs an enormous quantity of it, as is proved by introducing a very thin layer of water into the glass which contains the gas; for, in an instant, the whole acid gas disappears, and combines with the water.

This latter circumstance is taken advantage of in laboratories and manufactures, on purpose to obtain the acid of sea-salt in a liquid form; and for this purpose the apparatus (Pl. IV. Fig. 1.) is employed. It consists, 1st, of a tubulated retort A, into which the sea-salt, and after it the sulphuric acid, are introduced through the opening H; 2d, of the baloon or recipient c, b, intended for containing the small quantity of liquid which passes over during the process; and, 3d, of a set of bottles, with two mouths, L, L, L, L, half filled with water, intended for absorbing the gas disengaged by the distillation. This apparatus will be more amply described in the latter part of this work.

Although we have not yet been able, either to compose or to decompound this acid of sea-salt, we cannot have the smallest doubt that it, like all other acids, is composed by the union of oxygen with an acidifiable base. We have therefore called this unknown substance the muriatic base, or muriatic radical, deriving this name, after the example of Mr Bergman and Mr de Morveau, from the Latin word muria, which was anciently used to signify sea-salt. Thus, without being able exactly to determine the component parts of muriatic acid, we design, by that term, a volatile acid, which retains the form of gas in the common temperature and pressure of our atmosphere, which combines with great facility, and in great quantity, with water, and whose acidifiable base adheres so very intimately with oxygen, that no method has hitherto been devised for separating them. If ever this acidifiable base of the muriatic acid is discovered to be a known substance, though now unknown in that capacity, it will be requisite to change its present denomination for one analogous with that of its base.

In common with sulphuric acid, and several other acids, the muriatic is capable of different degrees of oxygenation; but the excess of oxygen produces quite contrary effects upon it from what the same circumstance produces upon the acid of sulphur. The lower degree of oxygenation converts sulphur into a volatile gasseous acid, which only mixes in small proportions with water, whilst a higher oxygenation forms an acid possessing much stronger acid properties, which is very fixed and cannot remain in the state of gas but in a very high temperature, which has no smell, and which mixes in large proportion with water. With muriatic acid, the direct reverse takes place; an additional saturation with oxygen renders it more volatile, of a more penetrating odour, less miscible with water, and diminishes its acid properties. We were at first inclined to have denominated these two degrees of saturation in the same manner as we had done with the acid of sulphur, calling the less oxygenated muriatous acid, and that which is more saturated with oxygen muriatic acid: But, as this latter gives very particular results in its combinations, and as nothing analogous to it is yet known in chemistry, we have left the name of muriatic acid to the less saturated, and give the latter the more compounded appellation of oxygenated muriatic acid.

Although the base or radical of the acid which is extracted from nitre or saltpetre be better known, we have judged proper only to modify its name in the same manner with that of the muriatic acid. It is drawn from nitre, by the intervention of sulphuric acid, by a process similar to that described for extracting the muriatic acid, and by means of the same apparatus (Pl. IV. Fig. 1.). In proportion as the acid passes over, it is in part condensed in the baloon or recipient, and the rest is absorbed by the water contained in the bottles L,L,L,L; the water becomes first green, then blue, and at last yellow, in proportion to the concentration of the acid. During this operation, a large quantity of oxygen gas, mixed with a small proportion of azotic gas, is disengaged.

This acid, like all others, is composed of oxygen, united to an acidifiable base, and is even the first acid in which the existence of oxygen was well ascertained. Its two constituent elements are but weakly united, and are easily separated, by presenting any substance with which oxygen has a stronger affinity than with the acidifiable base peculiar to this acid. By some experiments of this kind, it was first discovered that azote, or the base of mephitis or azotic gas, constituted its acidifiable base or radical; and consequently that the acid of nitre was really an azotic acid, having azote for its base, combined with oxygen. For these reasons, that we might be consistent with our principles, it appeared necessary, either to call the acid by the name of azotic, or to name the base nitric radical; but from either of these we were dissuaded, by the following considerations. In the first place, it seemed difficult to change the name of nitre or saltpetre, which has been universally adopted in society, in manufactures, and in chemistry; and, on the other hand, azote having been discovered by Mr Berthollet to be the base of volatile alkali, or ammoniac, as well as of this acid, we thought it improper to call it nitric radical. We have therefore continued the term of azote to the base of that part of atmospheric air which is likewise the nitric and ammoniacal radical; and we have named the acid of nitre, in its lower and higher degrees of oxygenation, nitrous acid in the former, and nitric acid in the latter state; thus preserving its former appellation properly modified.

Several very respectable chemists have disapproved of this deference for the old terms, and wished us to have persevered in perfecting a new chemical language, without paying any respect for ancient usage; so that, by thus steering a kind of middle course, we have exposed ourselves to the censures of one sect of chemists, and to the expostulations of the opposite party.

The acid of nitre is susceptible of assuming a great number of separate states, depending upon its degree of oxygenation, or upon the proportions in which azote and oxygen enter into its composition. By a first or lowest degree of oxygenation, it forms a particular species of gas, which we shall continue to name nitrous gas; this is composed nearly of two parts, by weight, of oxygen combined with one part of azote; and in this state it is not miscible with water. In this gas, the azote is by no means saturated with oxygen, but, on the contrary, has still a very great affinity for that element, and even attracts it from atmospheric air, immediately upon getting into contact with it. This combination of nitrous gas with atmospheric air has even become one of the methods for determining the quantity of oxygen contained in air, and consequently for ascertaining its degree of salubrity.

This addition of oxygen converts the nitrous gas into a powerful acid, which has a strong affinity with water, and which is itself susceptible of various additional degrees of oxygenation. When the proportions of oxygen and azote is below three parts, by weight, of the former, to one of the latter, the acid is red coloured, and emits copious fumes. In this state, by the application of a gentle heat, it gives out nitrous gas; and we term it, in this degree of oxygenation, nitrous acid. When four parts, by weight, of oxygen, are combined with one part of azote, the acid is clear and colourless, more fixed in the fire than the nitrous acid, has less odour, and its constituent elements are more firmly united. This species of acid, in conformity with our principles of nomenclature, is called nitric acid.

Thus, nitric acid is the acid of nitre, surcharged with oxygen; nitrous acid is the acid of nitre surcharged with azote; or, what is the same thing, with nitrous gas; and this latter is azote not sufficiently saturated with oxygen to possess the properties of an acid. To this degree of oxygenation, we have afterwards, in the course of this work, given the generical name of oxyd[14].

FOOTNOTES:

[12] The term formerly used by the English chemists for this acid was written sulphureous; but we have thought proper to spell it as above, that it may better conform with the similar terminations of nitrous, carbonous, &c. to be used hereafter. In general, we have used the English terminations ic and ous to translate the terms of the Author which end with ique and cux, with hardly any other alterations.—E.

[13] For this purpose, the operation called decrepitation is used, which consists in subjecting it to nearly a red heat, in a proper vessel, so as to evaporate all its water of crystallization.—E.

[14] In strict conformity with the principles of the new nomenclature, but which the Author has given his reasons for deviating from in this instance, the following ought to have been the terms for azote, in its several degrees of oxygenation: Azote, azotic gas, (azote combined with caloric), azotic oxyd gas, nitrous acid, and nitric acid.—E.



CHAP. VII.

Of the Decomposition of Oxygen Gas by means of Metals, and the Formation of Metallic Oxyds.

Oxygen has a stronger affinity with metals heated to a certain degree than with caloric; in consequence of which, all metallic bodies, excepting gold, silver, and platina, have the property of decomposing oxygen gas, by attracting its base from the caloric with which it was combined. We have already shown in what manner this decomposition takes place, by means of mercury and iron; having observed, that, in the case of the first, it must be considered as a kind of gradual combustion, whilst, in the latter, the combustion is extremely rapid, and attended with a brilliant flame. The use of the heat employed in these operations is to separate the particles of the metal from each other, and to diminish their attraction of cohesion or aggregation, or, what is the same thing, their mutual attraction for each other.

The absolute weight of metallic substances is augmented in proportion to the quantity of oxygen they absorb; they, at the same time, lose their metallic splendour, and are reduced into an earthy pulverulent matter. In this state metals must not be considered as entirely saturated with oxygen, because their action upon this element is counterbalanced by the power of affinity between it and caloric. During the calcination of metals, the oxygen is therefore acted upon by two separate and opposite powers, that of its attraction for caloric, and that exerted by the metal, and only tends to unite with the latter in consequence of the excess of the latter over the former, which is, in general, very inconsiderable. Wherefore, when metallic substances are oxygenated in atmospheric air, or in oxygen gas, they are not converted into acids like sulphur, phosphorus, and charcoal, but are only changed into intermediate substances, which, though approaching to the nature of salts, have not acquired all the saline properties. The old chemists have affixed the name of calx not only to metals in this state, but to every body which has been long exposed to the action of fire without being melted. They have converted this word calx into a generical term, under which they confound calcareous earth, which, from a neutral salt, which it really was before calcination, has been changed by fire into an earthy alkali, by losing half of its weight, with metals which, by the same means, have joined themselves to a new substance, whose quantity often exceeds half their weight, and by which they have been changed almost into the nature of acids. This mode of classifying substances of so very opposite natures, under the same generic name, would have been quite contrary to our principles of nomenclature, especially as, by retaining the above term for this state of metallic substances, we must have conveyed very false ideas of its nature. We have, therefore, laid aside the expression metallic calx altogether, and have substituted in its place the term oxyd, from the Greek word [Greek: oxys].

By this may be seen, that the language we have adopted is both copious and expressive. The first or lowest degree of oxygenation in bodies, converts them into oxyds; a second degree of additional oxygenation constitutes the class of acids, of which the specific names, drawn from their particular bases, terminate in ous, as the nitrous and sulphurous acids; the third degree of oxygenation changes these into the species of acids distinguished by the termination in ic, as the nitric and sulphuric acids; and, lastly, we can express a fourth, or highest degree of oxygenation, by adding the word oxygenated to the name of the acid, as has been already done with the oxygenated muriatic acid.

We have not confined the term oxyd to expressing the combinations of metals with oxygen, but have extended it to signify that first degree of oxygenation in all bodies, which, without converting them into acids, causes them to approach to the nature of salts. Thus, we give the name of oxyd of sulphur to that soft substance into which sulphur is converted by incipient combustion; and we call the yellow matter left by phosphorus, after combustion, by the name of oxyd of phosphorus. In the same manner, nitrous gas, which is azote in its first degree of oxygenation, is the oxyd of azote. We have likewise oxyds in great numbers from the vegetable and animal kingdoms; and I shall show, in the sequel, that this new language throws great light upon all the operations of art and nature.

We have already observed, that almost all the metallic oxyds have peculiar and permanent colours. These vary not only in the different species of metals, but even according to the various degrees of oxygenation in the same metal. Hence we are under the necessity of adding two epithets to each oxyd, one of which indicates the metal oxydated[15], while the other indicates the peculiar colour of the oxyd. Thus, we have the black oxyd of iron, the red oxyd of iron, and the yellow oxyd of iron; which expressions respectively answer to the old unmeaning terms of martial ethiops, colcothar, and rust of iron, or ochre. We have likewise the gray, yellow, and red oxyds of lead, which answer to the equally false or insignificant terms, ashes of lead, massicot, and minium.

These denominations sometimes become rather long, especially when we mean to indicate whether the metal has been oxydated in the air, by detonation with nitre, or by means of acids; but then they always convey just and accurate ideas of the corresponding object which we wish to express by their use. All this will be rendered perfectly clear and distinct by means of the tables which are added to this work.

FOOTNOTES:

[15] Here we see the word oxyd converted into the verb to oxydate, oxydated, oxydating, after the same manner with the derivation of the verb to oxygenate, oxygenated, oxygenating, from the word oxygen. I am not clear of the absolute necessity of this second verb here first introduced, but think, in a work of this nature, that it is the duty of the translator to neglect every other consideration for the sake of strict fidelity to the ideas of his author.—E.



CHAP. VIII.

Of the Radical Principle of Water, and of its Decomposition by Charcoal and Iron.

Until very lately, water has always been thought a simple substance, insomuch that the older chemists considered it as an element. Such it undoubtedly was to them, as they were unable to decompose it; or, at least, since the decomposition which took place daily before their eyes was entirely unnoticed. But we mean to prove, that water is by no means a simple or elementary substance. I shall not here pretend to give the history of this recent, and hitherto contested discovery, which is detailed in the Memoirs of the Academy for 1781, but shall only bring forwards the principal proofs of the decomposition and composition of water; and, I may venture to say, that these will be convincing to such as consider them impartially.

Experiment First.

Having fixed the glass tube EF, (Pl. vii. fig. 11.) of from 8 to 12 lines diameter, across a furnace, with a small inclination from E to F, lute the superior extremity E to the glass retort A, containing a determinate quantity of distilled water, and to the inferior extremity F, the worm SS fixed into the neck of the doubly tubulated bottle H, which has the bent tube KK adapted to one of its openings, in such a manner as to convey such aeriform fluids or gasses as may be disengaged, during the experiment, into a proper apparatus for determining their quantity and nature.

To render the success of this experiment certain, it is necessary that the tube EF be made of well annealed and difficultly fusible glass, and that it be coated with a lute composed of clay mixed with powdered stone-ware; besides which, it must be supported about its middle by means of an iron bar passed through the furnace, lest it should soften and bend during the experiment. A tube of China-ware, or porcellain, would answer better than one of glass for this experiment, were it not difficult to procure one so entirely free from pores as to prevent the passage of air or of vapours.

When things are thus arranged, a fire is lighted in the furnace EFCD, which is supported of such a strength as to keep the tube EF red hot, but not to make it melt; and, at the same time, such a fire is kept up in the furnace VVXX, as to keep the water in the retort A continually boiling.

In proportion as the water in the retort A is evaporated, it fills the tube EF, and drives out the air it contained by the tube KK; the aqueous gas formed by evaporation is condensed by cooling in the worm SS, and falls, drop by drop, into the tubulated bottle H. Having continued this operation until all the water be evaporated from the retort, and having carefully emptied all the vessels employed, we find that a quantity of water has passed over into the bottle H, exactly equal to what was before contained in the retort A, without any disengagement of gas whatsoever: So that this experiment turns out to be a simple distillation; and the result would have been exactly the same, if the water had been run from one vessel into the other, through the tube EF, without having undergone the intermediate incandescence.

Experiment Second.

The apparatus being disposed, as in the former experiment, 28 grs. of charcoal, broken into moderately small parts, and which has previously been exposed for a long time to a red heat in close vessels, are introduced into the tube EF. Every thing else is managed as in the preceding experiment.

The water contained in the retort A is distilled, as in the former experiment, and, being condensed in the worm, falls into the bottle H; but, at the same time, a considerable quantity of gas is disengaged, which, escaping by the tube KK, is received in a convenient apparatus for that purpose. After the operation is finished, we find nothing but a few atoms of ashes remaining in the tube EF; the 28 grs. of charcoal having entirely disappeared.

When the disengaged gasses are carefully examined, they are sound to weigh 113.7 grs.[16]; these are of two kinds, viz. 144 cubical inches of carbonic acid gas, weighing 100 grs. and 380 cubical inches of a very light gas, weighing only 13.7 grs. which takes fire when in contact with air, by the approach of a lighted body; and, when the water which has passed over into the bottle H is carefully examined, it is found to have lost 85.7 grs. of its weight. Thus, in this experiment, 85.7 grs. of water, joined to 28 grs. of charcoal, have combined in such a way as to form 100 grs. of carbonic acid, and 13.7 grs. of a particular gas capable of being burnt.

I have already shown, that 100 grs. of carbonic acid gas consists of 72 grs. of oxygen, combined with 28 grs. of charcoal; hence the 28 grs. of charcoal placed in the glass tube have acquired 72 grs. of oxygen from the water; and it follows, that 85.7 grs. of water are composed of 72 grs. of oxygen, combined with 13.7 grs. of a gas susceptible of combustion. We shall see presently that this gas cannot possibly have been disengaged from the charcoal, and must, consequently, have been produced from the water.

I have suppressed some circumstances in the above account of this experiment, which would only have complicated and obscured its results in the minds of the reader. For instance, the inflammable gas dissolves a very small part of the charcoal, by which means its weight is somewhat augmented, and that of the carbonic gas proportionally diminished. Altho' the alteration produced by this circumstance is very inconsiderable; yet I have thought it necessary to determine its effects by rigid calculation, and to report, as above, the results of the experiment in its simplified state, as if this circumstance had not happened. At any rate, should any doubts remain respecting the consequences I have drawn from this experiment, they will be fully dissipated by the following experiments, which I am going to adduce in support of my opinion.

Experiment Third.

The apparatus being disposed exactly as in the former experiment, with this difference, that instead of the 28 grs. of charcoal, the tube EF is filled with 274 grs. of soft iron in thin plates, rolled up spirally. The tube is made red hot by means of its furnace, and the water in the retort A is kept constantly boiling till it be all evaporated, and has passed through the tube EF, so as to be condensed in the bottle H.

No carbonic acid gas is disengaged in this experiment, instead of which we obtain 416 cubical inches, or 15 grs. of inflammable gas, thirteen times lighter than atmospheric air. By examining the water which has been distilled, it is found to have lost 100 grs. and the 274 grs. of iron confined in the tube are found to have acquired 85 grs. additional weight, and its magnitude is considerably augmented. The iron is now hardly at all attractable by the magnet; it dissolves in acids without effervescence; and, in short, it is converted into a black oxyd, precisely similar to that which has been burnt in oxygen gas.

In this experiment we have a true oxydation of iron, by means of water, exactly similar to that produced in air by the assistance of heat. One hundred grains of water having been decomposed, 85 grs. of oxygen have combined with the iron, so as to convert it into the state of black oxyd, and 15 grs. of a peculiar inflammable gas are disengaged: From all this it clearly follows, that water is composed of oxygen combined with the base of an inflammable gas, in the respective proportions of 85 parts, by weight of the former, to 15 parts of the latter.

Thus water, besides the oxygen, which is one of its elements in common with many other substances, contains another element as its constituent base or radical, and for which we must find an appropriate term. None that we could think of seemed better adapted than the word hydrogen, which signifies the generative principle of water, from [Greek: ydor] aqua, and [Greek: geinomas] gignor[17]. We call the combination of this element with caloric hydrogen gas; and the term hydrogen expresses the base of that gas, or the radical of water.

This experiment furnishes us with a new combustible body, or, in other words, a body which has so much affinity with oxygen as to draw it from its connection with caloric, and to decompose air or oxygen gas. This combustible body has itself so great affinity with caloric, that, unless when engaged in a combination with some other body, it always subsists in the aeriform or gasseous state, in the usual temperature and pressure of our atmosphere. In this state of gas it is about 1/13 of the weight of an equal bulk of atmospheric air; it is not absorbed by water, though it is capable of holding a small quantity of that fluid in solution, and it is incapable of being used for respiration.

As the property this gas possesses, in common with all other combustible bodies, is nothing more than the power of decomposing air, and carrying off its oxygen from the caloric with which it was combined, it is easily understood that it cannot burn, unless in contact with air or oxygen gas. Hence, when we set fire to a bottle full of this gas, it burns gently, first at the neck of the bottle, and then in the inside of it, in proportion as the external air gets in: This combustion is slow and successive, and only takes place at the surface of contact between the two gasses. It is quite different when the two gasses are mixed before they are set on fire: If, for instance, after having introduced one part of oxygen gas into a narrow mouthed bottle, we fill it up with two parts of hydrogen gas, and bring a lighted taper, or other burning body, to the mouth of the bottle, the combustion of the two gasses takes place instantaneously with a violent explosion. This experiment ought only to be made in a bottle of very strong green glass, holding not more than a pint, and wrapped round with twine, otherwise the operator will be exposed to great danger from the rupture of the bottle, of which the fragments will be thrown about with great force.

If all that has been related above, concerning the decomposition of water, be exactly conformable to truth;—if, as I have endeavoured to prove, that substance be really composed of hydrogen, as its proper constituent element, combined with oxygen, it ought to follow, that, by reuniting these two elements together, we should recompose water; and that this actually happens may be judged of by the following experiment.

Experiment Fourth.

I took a large cristal baloon, A, Pl. iv. fig. 5. holding about 30 pints, having a large opening, to which was cemented the plate of copper BC, pierced with four holes, in which four tubes terminate. The first tube, H h, is intended to be adapted to an air pump, by which the baloon is to be exhausted of its air. The second tube gg, communicates, by its extremity MM, with a reservoir of oxygen gas, with which the baloon is to be filled. The third tube d D d', communicates, by its extremity d NN, with a reservoir of hydrogen gas. The extremity d' of this tube terminates in a capillary opening, through which the hydrogen gas contained in the reservoir is forced, with a moderate degree of quickness, by the pressure of one or two inches of water. The fourth tube contains a metallic wire GL, having a knob at its extremity L, intended for giving an electrical spark from L to d', on purpose to set fire to the hydrogen gas: This wire is moveable in the tube, that we may be able to separate the knob L from the extremity d' of the tube D d'. The three tubes d D d', gg, and H h, are all provided with stop-cocks.

That the hydrogen gas and oxygen gas may be as much as possible deprived of water, they are made to pass, in their way to the baloon A, through the tubes MM, NN, of about an inch diameter, and filled with salts, which, from their deliquescent nature, greedily attract the moisture of the air: Such are the acetite of potash, and the muriat or nitrat of lime[18]. These salts must only be reduced to a coarse powder, lest they run into lumps, and prevent the gasses from geting through their interstices.

We must be provided before hand with a sufficient quantity of oxygen gas, carefully purified from all admixture of carbonic acid, by long contact with a solution of potash[19].

We must likewise have a double quantity of hydrogen gas, carefully purified in the same manner by long contact with a solution of potash in water. The best way of obtaining this gas free from mixture is, by decomposing water with very pure soft iron, as directed in Exp. 3. of this chapter.

Having adjusted every thing properly, as above directed, the tube H h is adapted to an air-pump, and the baloon A is exhausted of its air. We next admit the oxygen gas so as to fill the baloon, and then, by means of pressure, as is before mentioned, force a small stream of hydrogen gas through its tube D d', which we immediately set on fire by an electric spark. By means of the above described apparatus, we can continue the mutual combustion of these two gasses for a long time, as we have the power of supplying them to the baloon from their reservoirs, in proportion as they are consumed. I have in another place[20] given a description of the apparatus used in this experiment, and have explained the manner of ascertaining the quantities of the gasses consumed with the most scrupulous exactitude.

In proportion to the advancement of the combustion, there is a deposition of water upon the inner surface of the baloon or matrass A: The water gradually increases in quantity, and, gathering into large drops, runs down to the bottom of the vessel. It is easy to ascertain the quantity of water collected, by weighing the baloon both before and after the experiment. Thus we have a twofold verification of our experiment, by ascertaining both the quantities of the gasses employed, and of the water formed by their combustion: These two quantities must be equal to each other. By an operation of this kind, Mr Meusnier and I ascertained that it required 85 parts, by weight, of oxygen, united to 15 parts of hydrogen, to compose 100 parts of water. This experiment, which has not hitherto been published, was made in presence of a numerous committee from the Royal Academy. We exerted the most scrupulous attention to its accuracy; and have reason to believe that the above propositions cannot vary a two hundredth part from absolute truth.

From these experiments, both analytical and synthetic, we may now affirm that we have ascertained, with as much certainty as is possible in physical or chemical subjects, that water is not a simple elementary substance, but is composed of two elements, oxygen and hydrogen; which elements, when existing separately, have so strong affinity for caloric, as only to subsist under the form of gas in the common temperature and pressure of our atmosphere.

This decomposition and recomposition of water is perpetually operating before our eyes, in the temperature of the atmosphere, by means of compound elective attraction. We shall presently see that the phenomena attendant upon vinous fermentation, putrefaction, and even vegetation, are produced, at least in a certain degree, by decomposition of water. It is very extraordinary that this fact should have hitherto been overlooked by natural philosophers and chemists: Indeed, it strongly proves, that, in chemistry, as in moral philosophy, it is extremely difficult to overcome prejudices imbibed in early education, and to search for truth in any other road than the one we have been accustomed to follow.

I shall finish this chapter by an experiment much less demonstrative than those already related, but which has appeared to make more impression than any other upon the minds of many people. When 16 ounces of alkohol are burnt in an apparatus[21] properly adapted for collecting all the water disengaged during the combustion, we obtain from 17 to 18 ounces of water. As no substance can furnish a product larger than its original bulk, it follows, that something else has united with the alkohol during its combustion; and I have already shown that this must be oxygen, or the base of air. Thus alkohol contains hydrogen, which is one of the elements of water; and the atmospheric air contains oxygen, which is the other element necessary to the composition of water. This experiment is a new proof that water is a compound substance.

FOOTNOTES:

[16] In the latter part of this work will be found a particular account of the processes necessary for separating the different kinds of gasses, and for determining their quantities.—A.

[17] This expression Hydrogen has been very severely criticised by some, who pretend that it signifies engendered by water, and not that which engenders water. The experiments related in this chapter prove, that, when water is decomposed, hydrogen is produced, and that, when hydrogen is combined with oxygen, water is produced: So that we may say, with equal truth, that water is produced from hydrogen, or hydrogen is produced from water.—A.

[18] See the nature of these salts in the second part of this book.—A.

[19] By potash is here meant, pure or caustic alkali, deprived of carbonic acid by means of quick-lime: In general, we may observe here, that all the alkalies and earths must invariably be considered as in their pure or caustic state, unless otherwise expressed.—E. The method of obtaining this pure alkali of potash will be given in the sequel.—A.

[20] See the third part of this work.—A.

[21] See an account of this apparatus in the third part of this work.—A.



CHAP. IX.

Of the quantities of Caloric disengaged from different species of Combustion.

We have already mentioned, that, when any body is burnt in the center of a hollow sphere of ice and supplied with air at the temperature of zero (32 deg.), the quantity of ice melted from the inside of the sphere becomes a measure of the relative quantities of caloric disengaged. Mr de la Place and I gave a description of the apparatus employed for this kind of experiment in the Memoirs of the Academy for 1780, p. 355; and a description and plate of the same apparatus will be found in the third part of this work. With this apparatus, phosphorus, charcoal, and hydrogen gas, gave the following results:

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